Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
Intramolecular charge separation in a hydrogen bonded tyrosineruthenium(II)-naphthalene diimide triad
Olof Johansson,a Henriette Wolpher,a Magnus Borgström,b Leif Hammarström,b Jonas
Bergquist,c Licheng Sun,a Björn Åkermarka*
a
Department of Organic Chemistry, Stockholm University, 106 91 Stockholm,
Sweden; E-mail: bjorn.akermark@organ.su.se
b
Department of Physical Chemistry, Uppsala University, P.O. Box 579, 751 23
Uppsala, Sweden; E-mail: Leifh@fki.uu.se
c
Department of Analytical Chemistry, Uppsala University, P.O. Box 599, 751 24
Uppsala, Sweden
SUPPORTING INFORMATION
Experimental Section
General. The compounds bpyPhNDI (1),1 bpyAla (2),2 bpyTyr (3),2 bpyCOOH (4),3
dpaTyr (5),4 Boc-dpaTyr (6),4 and Ru(DMSO)4Cl25 were prepared as described
elsewhere. All solvents were used as received except DMF (dried over molecular
sieves prior to use) and THF (freshly distilled from Na/benzophenone).
N
N
O
O
N
N
N
N
N
O
N
CON
H
O
1
OH
CON
H
CO 2Et
2
N
N
N
N
N
N
OH
N
CO 2Et
N
N
BocHN
CO 2Et
5
N
N
N
4
N
OH
H2N
COOH
CO 2Et
3
N
6
Ru(bpyPhNDI)2Cl2 (7). BpyPhNDI (1) (0.252 g, 0.41 mmol), Ru(DMSO)4Cl2 (0.100
g, 0.21 mmol), and LiCl (0.090 g, 2.1 mmol), were dissolved in DMF (20 mL) and the
solution was heated at reflux under nitrogen for 3 hours. The dark purple solution was
cooled to room temperature and the solvent was removed. Water was added and the
mixture was filtered. The remaining purple solid was washed with several portions of
H2O and Et2O. The solid was not further purified (0.272 g, 93 %). MS (MALDI-TOF,
dihydroxybenzoic acid (DHB) as matrix): Found [M-Cl]+ 1353.3 m/z (calc. for
C76H64N8O8RuCl: 1353.4), [M-2Cl+D]+ 1471.3 m/z (calc. for C83H69N8O12Ru:
1471.4).
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
[Ru(bpyPhNDI)2(bpyAla)][PF6]2 (Ala-Ru-NDI). Compounds 7 (0.200 g, 0.14
mmol) and 2 (0.046 g, 0.15 mmol) were added to EtOH (30 mL). The solution was
degassed and the mixture heated at reflux under nitrogen in the dark for 24 hours. The
mixture was filtered, the solvent removed, and the remaining solid chromatographed
on silica gel (eluent: CH3CN/H2O/sat. KNO3, 95:5:1). Fractions containing product
were combined and the solvent removed. Water, CH2Cl2, and an excess of NH4PF6
were added and the mixture was left stirring. The organic phase was separated and
washed with additional H2O, dried over Na2SO4, and the solvent removed to give
Ala-Ru-NDI (0.080 g, 29 %). 1H NMR (400 MHz, CD3CN, 25 C):  9.00-7.20
(37H), (N-H at 7.69 (d)), 4.61 (m, 1H, CHNH), 4.18 (m, 2H, CO2CH2CH3), 4.10 (m,
4H, NDI-CH2-R), 2.59 (m, 3H, CH3bpy), ~1.9 (m, 2H, NDI-R), 1.52 (m, 3H,
CHCH3), 1.45-1.30 (m, 16H, NDI-R), 1.25 (t, 3H, CO2CH2CH3), 0.94 (t, 6H, NDI-R),
0.89 (t, 6H, NDI-R); ESI-MS: m/z [M-PF6]+ 1776.51 (calc. for C93H83N11O11RuPF6:
1776.50), [M-2PF6]2+ 815.77 (calc. for C93H83N11O11Ru: 815.77); elemental analysis
calc. (%) for C93H83N11O11RuP2F12H2O: C 57.58, H 4.42, N 7.94; found C 57.44, H
4.54, N 7.76.
2+
N
N
Ru
N
O
N
CON
H
2
N
O
CO 2Et
O
N
Ala-Ru-NDI
O
Ru(bpyPhNDI)2(bpyTyr)PF62 (Tyr-Ru-NDI). Compounds 7 (0.220 g, 0.16
mmol) and 3 (0.063 g, 0.16 mmol) were added to EtOH (30 mL). The solution was
degassed and the mixture heated at reflux in the dark for 24 hours. The solvent was
removed and the residue chromatographed on silica (eluent: CH3CN/H2O/sat. KNO3,
90:2:1) Fractions containing product were combined and the solvent removed. The
product was redissolved in a small amount of acetone and precipitated by addition of
NH4PF6 in H2O. The precipitate was filtered off, washed with H2O and dried in a
desiccator giving Tyr-Ru-NDI (0.120 g, 35 %). 1H NMR (400 MHz, CD3CN, 25°C):
δ 8.90-7.30 (37H), (N-H at 7.69 (d)), 7.13 (dd, 2H, Tyr-ArH) 6.74 (dd, 2H, Tyr-ArH),
6.90 (1H, TyrOH ), 4.85 (m, 1H, CHNH), 4.18 (m, 2H, CO2CH2CH3), 4.11 (m, 4H,
NDI-CH2-R), 3.23 (dd, 1H, CHCH2Ar) 3.10 (dd, 1H, CHCH2Ar), 2.62 (m, 3H,
CH3bpy), ~1.9 (m, 2H, NDI-R), 1.45-1.30 (m, 16H, NDI-R), 1.25 (t, 3H,
CO2CH2CH3), 0.96 (t, 6H, NDI-R), 0.90 (t, 6H, NDI-R); ESI-MS: m/z [M-2PF6]2+
861.79 (calc. for C99H87N11O12Ru: 861.78); elemental analysis calc. (%) for
C99H87F12N11O12P2Ru: C 59.05, H 4.35, N 7.65; found C 59.04, H 4.65, N 7.40.
2+
N
N
Ru
N
O
N
2
N
O
O
N
Tyr-Ru-NDI
O
OH
CON
H
CO 2Et
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
[Ru(bpyPhNDI)2(bpyCOOH)][PF6]2 (8). This complex was prepared as Ala-RuNDI above. Compounds 7 (0.316 g, 0.23 mmol) and 4 (0.052 g, 0.24 mmol) gave
after chromatography (silica, eluent: CH3CN/H2O/sat. KNO3, 20:3:1) 8 (0.123 g, 30
%). 1H NMR (400 MHz, CD3CN, 25 C):  9.00-7.20 (36H), 4.09 (m, 4H, NDI-CH2R), 2.56 (s, 3H, CH3bpy), ~1.9 (m, 2H, NDI-R), 1.50-1.25 (m, 16H, NDI-R), 1.000.85 (m, 12H, NDI-R); MS (MALDI-TOF): Found [M-PF6]+ 1677.1 m/z (calc. for
C88H74N10O10RuPF6: 1677.4), [M-2PF6+e]+ 1532.3 m/z (calc. for C88H74N10O10Ru:
1532.5).
2+
N
N
Ru
N
O
N
COOH
2
N
O
O
8
N
O
[Ru(bpyPhNDI)2(bpy-dpaTyr)][PF6]2 (dpaTyr-Ru-NDI). Complex 8 (0.319 g,
0.175 mmol) was dissolved in freshly distilled SOCl2 (20 mL) and the solution was
left stirring under nitrogen atmosphere at room temperature in the dark for 15 hours.
The SOCl2 was removed and the resulting solid was redissolved in dry CH2Cl2 (15
mL). Compound 5 (0.126 g, 0.199 mmol) in CH2Cl2 (5 mL) and NEt3 (0.2 mL) were
added and the solution was left stirring over night under a nitrogen atmosphere. To
the solution, H2O (20 mL) and an excess of NH4PF6 were added. The organic phase
was separated, the solvent removed, and the residue chromatographed on silica
(eluent: CH3CN, H2O, sat. KNO3, 40:4:1). The second band was collected and the
solvent removed. Water, CH2Cl2, and an excess of NH4PF6 were added. The organic
phase was separated and washed with sat. Na2CO3 and H2O. After drying over
Na2SO4, the solvent was removed to give dpaTyr-Ru-NDI (0.217 g, 51 %). 1H NMR
(400 MHz, CD3CN, 25 C):  11.03 (s, 1H, TyrOH), 8.90-7.00 (55H), 4.92 (m, 1H,
CHNH), 4.20-4.05 (m, 6H, CO2CH2CH3 + NDI-CH2-R), 3.75-3.50 (m, 12H, CH2N),
3.20-3.00 (m, 2H, CHCH2Ar), 2.48 (m, 3H, CH3bpy), ~1.9 (m, 2H, NDI-R), 1.451.25 (m, 16H, NDI-R), 1.25-1.15 (m, 3H, CO2CH2CH3), 0.94 (t, 6H, NDI-R), 0.89 (t,
6H, NDI-R); ESI-MS: m/z [M-PF6]2+ 1145.91 (calc. for C125H114N17O12RuPF6:
1145.88), [M-2PF6]2+ 1072.91 (calc. for C125H113N17O12Ru: 1072.89); elemental
analysis calc. (%) for C125H113N17O12RuP2F123H2O: C 60.29, H 4.82, N 9.56; found
C 60.39, H 4.83, N 9.54.
2+
N
N
N
N
Ru
N
O
N
2
N
O
dpaTyr-Ru-NDI
O
CON
H
CO 2Et
N
N
N
O
N
N
OH
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
Boc-dpaTyr(Me) (9). Compound 6 (0.310 g, 0.42 mmol) and potassium tert-butoxide
(0.047 g, 0.42 mmol) were added to THF (4 mL) under a nitrogen atmosphere. After
45 min, CH3I in THF (1.5 mL) was added and the solution was stirred at room
temperature for 3.5 hours. The solvent was removed, the residue redissolved in
CH2Cl2 and washed with H2O. After drying over Na2SO4 and removal of solvent, the
residue was chromatographed on silica (eluent: CH3CN/NH3 (25 %) 10:1) to give 9
(0.177 g, 56 %). 1H NMR (400 MHz, CDCl3, 25 C):  8.50 (m, 4H), 7.63 (dt, 4H),
7.52 (d, 4H), 7.36 (s, 2H), 7.10 (ddd, 4H), 5.59 (d, 1H), 4.53 (m, 1H), 4.02 (m, 2H),
3.78 (s, 8H), 3.68 (s, 4H), 3.51 (s, 3H), 3.05 (m, 2H), 1.28 (s, 9H), 1.08 (t, 3H).
N
N
N
O
9
BocHN
CO 2Et
N
N
N
dpaTyr(Me) (10). Compound 9 (0.170 g, 0.23 mmol) was dissolved in dry CH2Cl2 (5
mL) under a nitrogen atmosphere. The temperature was reduced to 0 C and
trifluoroacetic acid (5 mL) was added dropwise. The solution was left at room
temperature for 4 hours. The solvent was removed, the residue dissolved in CH2Cl2
and washed with NH3 (25 %). After drying over Na2SO4, the solvent was removed to
give 10 (0.137 g, 93 %). 1H NMR (300 MHz, CDCl3, 25 C):  8.48 (m, 4H), 7.62
(dt, 4H), 7.54 (d, 4H), 7.35 (s, 2H), 7.10 (ddd, 4H), 4.06 (m, 2H), 3.78 (s, 8H), 3.69
(s, 4H), 3.66 (m, 1H), 3.53 (s, 3H), 3.03 (dd, 1H), 2.80 (dd, 1H), 1.14 (t, 3H).
N
N
N
O
10
H2N
CO 2Et
N
N
N
[Ru(bpyPhNDI)2(bpy-dpaTyr(Me))][PF6]2 (dpaTyr(Me)-Ru-NDI). This complex
was prepared as dpaTyr-Ru-NDI above. Complex 8 (0.118 g, 0.065 mmol) and 10
(0.050 g, 0.077 mmol) gave dpaTyr(Me)-Ru-NDI (0.043 g, 27 %). 1H NMR (300
MHz, CD3CN, 25 C):  8.90-7.00 (55H), 5.00 (m, 1H, CHNH), 4.20-4.00 (m, 6H,
CO2CH2CH3 + NDI-CH2-R), 3.75-3.50 (m, 15H, CH2N + TyrOCH3), 3.30-3.10 (m,
2H, CHCH2Ar), 2.60-2.40 (m, 3H, CH3bpy), ~1.9 (m, 2H, NDI-R), 1.45-1.25 (m,
16H, NDI-R), 1.25-1.15 (m, 3H, CO2CH2CH3), 0.94 (t, 6H, NDI-R), 0.89 (t, 6H,
NDI-R); ESI-MS: m/z [M-PF6]2+ 1152.96 (calc. for C126H116N17O12RuPF6:
1152.88), [M-2PF6]2+ 1079.96 (calc. for C126H115N17O12 Ru: 1079.90).
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
2+
N
N
N
N
Ru
N
O
2
N
O
N
CON
H
CO 2Et
N
N
N
O
N
N
O
dpaTyr(Me)-Ru-NDI
O
Reference List
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Sundström, Inorg. Chem., 2002, 41, 6258.
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(5) I. P. Evans, A. Spencer and G. Wilkinson, J. Chem. Soc. Dalton Trans., 1973, 204.